JP2840866B2 - Adhesive composition of nitrile group-containing highly saturated copolymer rubber and organic synthetic fiber - Google Patents

Description

The present invention relates to an adhesive composition of a nitrile group-containing highly saturated copolymer rubber and an organic synthetic fiber, a method for treating an organic synthetic fiber using the same, and an organic synthetic fiber. And a method for bonding rubber to rubber.

[Conventional technology]

Composites of fibers and rubber are used for automotive timing belts, polyribbed belts, conveyor belts, hoses, diaphragms and the like. As rubber for that,
Conventionally, oil-resistant acrylonitrile-butadiene copolymer rubber has been used. However, in recent years, in response to emission regulations for automobiles, downsizing of the engine room to reduce vehicle weight, and sealing of the engine room to reduce noise,
Heat resistance is required in addition to oil resistance.
For this reason, recently, nitrile group-containing highly saturated copolymer rubbers having both heat resistance and oil resistance have been used for the above-mentioned applications. Correspondingly, there has been a demand for a good adhesive between the nitrile group-containing highly saturated copolymer rubber and the fiber.

The present inventors have proposed an adhesive composition comprising a nitrile group-containing highly saturated copolymer rubber latex and an organic synthetic fiber, which contains a nitrile group-containing highly saturated copolymer rubber latex as one component (Japanese Patent Application Laid-Open No. Sho 63-163). 248879), but further investigation revealed that α, β
-When a latex obtained by a phase inversion method from an organic solvent solution of a nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating an ethylenically unsaturated nitrile-conjugated diene copolymer rubber, a belt molded product is used. Although the adhesive strength at the time of production (initial adhesive strength) and the adhesive strength after high temperature use (heat resistant adhesive strength) are at a satisfactory level, the adhesive strength after immersion in hot water (water resistant adhesive strength) is not sufficient. Clearly came.

[Problems to be solved by the invention]

An object of the present invention is to provide an adhesive composition of a nitrile group-containing highly saturated copolymer rubber and an organic synthetic fiber which is excellent in initial adhesive strength, heat resistant adhesive strength and water resistant adhesive strength. Another object of the present invention is to provide a method for treating fibers with the adhesive composition. Another object of the present invention is
An object of the present invention is to provide a method for bonding an organic synthetic fiber to a nitrile group-containing highly saturated copolymer rubber.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve these objects, and as a result, obtained by hydrogenating a nitrile group-containing unsaturated copolymer rubber by a specific method, a nitrile group-containing highly saturated copolymer rubber latex. In the case of using, it was found that the above-mentioned water-resistant adhesive strength was improved, and the present invention was completed based on this finding.

Thus, according to the present invention, an iodine value containing a nitrile group-containing highly saturated copolymer rubber latex having a value of 120 or less and a resorcinol-formaldehyde resin, an adhesion between an organic synthetic fiber and a nitrile group-containing highly saturated copolymer rubber, In the agent composition, the nitrile group-containing highly saturated copolymer rubber latex is obtained by treating the nitrile group-containing unsaturated copolymer rubber latex obtained by the emulsion polymerization method with hydrogen in the presence of a hydrogenation catalyst. An adhesive composition characterized by being obtained by selectively hydrogenating a carbon-carbon double bond in a nitrile group-containing unsaturated copolymer constituting a latex, the adhesive composition comprising: A method for treating an organic synthetic fiber characterized by treating, and a nitrile group-containing highly saturated copolymer rubber characterized by treating an organic synthetic fiber with the adhesive composition. Vulcanization method is provided with machine synthetic fibers.

(Nitrile Group-Containing Unsaturated Copolymer Rubber Latex) The nitrile group-containing unsaturated copolymer rubber latex used in the present invention is obtained by copolymerizing a conjugated diene with an α, β-ethylenically unsaturated nitrile, if desired. A latex of a copolymer rubber containing a possible ethylenically unsaturated monomer as a third component, which is obtained by emulsion-copolymerizing these monomers.

In this copolymer rubber, the constitutional ratio of each monomer is 30 to 90 parts by weight of a conjugated diene unit, 10 to 50 parts by weight of an α, β-ethylenically unsaturated nitrile unit, and 0 to 50 parts by weight of an ethylenically unsaturated monomer unit. ~ 20 parts by weight.

 The molecular weight of the copolymer rubber is not particularly limited.

The α, β-ethylenically unsaturated nitrile may be any as long as it contains a nitrile group and a polymerizable unsaturated bond. Specific examples thereof include acrylonitrile and methacrylonitrile.

The conjugated diene is not particularly limited, but specific examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,
Aliphatic conjugated dienes such as 3-butadiene, 1,3-pentadiene and halogen-substituted butadiene can be shown. These conjugated dienes may be used alone or in combination of two or more.

The ethylenically unsaturated monomer includes the conjugated diene and α,
Any one can be used as long as it can be emulsion-copolymerized with β-ethylenically unsaturated nitrile. Specific examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid, and salts thereof; ) Methyl acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Trifluoroethyl acrylate, tetrafluoropropyl (meth) acrylate, ethyl itaconate, butyl fumarate, butyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth)
Methoxyethoxyethyl acrylate, cyanomethyl (meth) acrylate, 2-dianoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, (meth)
2-ethyl-6-cyanohexyl acrylate, (meth)
Unsaturated carboxylic esters such as 3-cyanopropyl acrylate, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-
(Meth) acrylamide and N-substituted derivatives such as dimethylol (meth) acrylamide and N-ethoxymethyl (meth) acrylamide; fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; vinyl pyridine and the like. Further, N- (4-anilinophenyl) (meth) acrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilinophenyl)
Crotonamide, N- (4-anilinophenyl) amino-2-hydroxypropyl (meth) allyl ether,
5-N- (4-anilinophenyl) (meth) acrylate
Amino-2-hydroxypentyl, 2-N- (4-anilinophenyl) aminoethyl (meth) acrylate, N-
[4- (methylanilino) phenyl] (meth) acrylamide, N- (4-anilinophenyl) maleimide,
N- [4- (methylanilino) phenyl] maleimide, N-phenyl-4- (3-vinylbenzyloxy)
Copolymerizable antioxidants such as aniline and N-phenyl-4- (4-vinylbenzyloxy) aniline can also be copolymerized. In the present invention, non-conjugated dienes such as vinyl norbornene, dicyclopentadiene and 1,4-hexadiene are also included in the ethylenically unsaturated monomers.

Specific examples of such a nitrile-co-containing unsaturated copolymer rubber include butadiene-acrylonitrile copolymer rubber, isoprene-butadiene-acrylonitrile copolymer rubber, isoprene-acrylonitrile copolymer rubber;
Butadiene-methyl acrylate-acrylonitrile copolymer rubber, butadiene-acrylic acid-acrylonitrile copolymer rubber, butadiene-ethylene-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl acrylate-vinyl norbornene-acrylonitrile copolymer Rubber and the like.

In the present invention, the method of emulsion polymerization of the monomer,
A conventionally known method may be adopted. That is, the emulsion polymerization system may be any of a batch system, a semi-batch system, and a continuous system, and the polymerization temperature and pressure are not limited.

The emulsifier used at the time of polymerization is not particularly limited, and anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used. Among them, anionic surfactants, especially fatty acids Systems are preferred. The amount of the latex is not particularly limited, but it is in the range of 1 to 10% by weight, preferably 2 to 6% by weight based on the total amount of the monomers from the viewpoint of the adhesive strength of the adhesive composition obtained from this latex.

Further, a polymerization initiator, a molecular weight modifier and other polymerization auxiliary materials may also be those which are usually used.

Further, an antioxidant, a pH adjuster and the like may be added to the latex obtained by the polymerization, if necessary.

(Hydrogenation) The nitrile group-containing highly saturated copolymer rubber latex used in the present invention is obtained by treating a nitrile group-containing unsaturated copolymer rubber latex obtained by an emulsion polymerization method with hydrogen in the presence of a hydrogenation catalyst. As a result, the latex can be obtained by selectively hydrogenating the carbon-carbon double bond of the nitrile group-containing unsaturated copolymer.

The treatment of the latetsk with hydrogen (hydrogenation reaction) is carried out by enclosing the latex, the hydrogenation catalyst and hydrogen in a pressure-resistant container, preferably with stirring. The order of these additions is not particularly limited, but it is generally preferable from the viewpoint of operation that latex is charged first and hydrogen is sealed last.

The concentration of the latex to be subjected to the hydrogenation reaction is not particularly limited, but is preferably 20% by weight or less in terms of solid content. If it exceeds 20% by weight, the average particle size of the latex increases, and a coagulation tends to occur.

In the hydrogenation, the stability can be improved by adding a surfactant to the latex obtained by the emulsion polymerization method. As the surfactant for this purpose, the same as the above-mentioned emulsifier for polymerization can be used. Its usage is
In order not to lower the adhesive strength characteristics of the desired adhesive composition, the content is preferably 4% or less based on the weight of the copolymer.

The hydrogenation catalyst used in the present invention is not particularly limited as long as it is a palladium compound that is not easily decomposed by water.

Specific examples thereof include, for example, palladium salts of carboxylic acids such as formic acid, acetic acid, propionic acid, lauric acid, succinic acid, stearic acid, oleic acid, phthalic acid and benzoic acid; palladium chloride, dichloro (cyclooctadiene)
Chlorinated palladium such as palladium, dichloro (norbornadiene) palladium, dichloro (benzonitrile) palladium, dichlorobis (triphenylphosphine) palladium, ammonium tetrachloropalladium (II), ammonium hexachloropalladium (IV); palladium bromide, etc. Various organic compounds, inorganic compounds and complex salts such as bromide; iodide such as palladium iodide; palladium sulfate dihydrate; potassium tetracyanopalladium (II) acid acid hydrate; It is not something to be done. Among these, palladium salts of carboxylic acids, dichloro (norbornadiene) palladium, ammonium hexachloropalladate and the like are particularly preferred.

The amount of these catalysts may be appropriately determined depending on the type of the copolymer to be hydrogenated and the intended hydrogenation rate, but is usually 5 to 6,000 per weight of the nitrile group-containing unsaturated copolymer.
0 ppm, preferably 10 to 4,000 ppm. Although 6,000 ppm or more may be used, it is not economical.

The method of adding the hydrogenation catalyst is not particularly limited, and may be added as a solid, or may be added in a state of being decomposed into water or latex, but when the hydrogenation catalyst is dissolved in an organic solvent. Is preferably added to the latex of the nitrile group-containing unsaturated copolymer as a solution of the hydrogenation catalyst in an organic solvent, from the viewpoint of the efficiency of the hydrogenation reaction and the operation.

In the present invention, the hydrogenation reaction can be carried out efficiently by adding an organic solvent capable of dissolving or swelling the nitrile group-containing unsaturated copolymer to the reaction system. This is thought to be because the nitrile group-containing unsaturated copolymer constituting the latex swells with the organic solvent, and as a result, the hydrogenation catalyst easily approaches the carbon-carbon double bond in the copolymer. Can be

Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene;
Halogenated hydrocarbons such as dichloroethane, chloroform, chlorobenzene, and carbon tetrachloride; ketones such as methyl ethyl ketone, acetone, cyclohexanone, and cyclopentanone; methyl acetate, ethyl acetate, propyl acetate;
Carboxylic acid esters such as butyl acetate; alcohols having 6 or more carbon atoms such as diacetone alcohol and benzyl alcohol; ethers such as dioxane, tetrahydrofuran and ethyl ether; nitriles such as acetonitrile, acrylonitrile and propionitrile. Of these, ketones and carboxylic esters are preferred. Each of these organic solvents, alone,
Alternatively, two or more kinds can be used in combination.

The amount of the organic solvent used is 3 to the latex in volume ratio.
It is at most 1.5 times, preferably at most 1.5 times, more preferably at most equal to 0.05 times. Even if the amount exceeds 3 times, the hydrogenation reaction proceeds, but the emulsion is destroyed and easily separated into a solvent phase and an aqueous phase. A new process, such as recovery of waste, is required. In the range of 3 times to 1.5 times, although the hydrogenation reaction can be performed while maintaining the emulsion state, the latex particle diameter increases during the reaction and the emulsion may be destroyed after the reaction.

The timing of adding the organic solvent may be before, after or simultaneously with the addition of the hydrogenation catalyst.

The hydrogenation reaction temperature is 0 to 300 ° C, preferably 20 to 150 ° C.
It is. Although 150 ° C. or more may be used, side reactions other than the selective hydrogenation of the target carbon-carbon double bond, such as hydrogenation of an organic solvent and hydrogenation of a nitrile group, are likely to occur.

As a hydrogen source for the hydrogenation reaction, gaseous hydrogen or dissolved hydrogen is dissolved. Contact between hydrogen and the carbon-carbon double bond in the nitrile-drop group-containing unsaturated copolymer can be easily achieved by, for example, stirring the reaction system.

Hydrogen pressure used is atmospheric ~300kg / cm ^2, preferably in the range 5~200kg / cm ^2, more preferably of 10~80kg / cm ^2. A high pressure of 300 kg / cm ² or more is acceptable, but it is not practical because equipment costs are high and handling is troublesome.

The hydrogenation rate (i.e., the iodine value of the nitrile group-containing copolymer) may be controlled by any method, but usually, the hydrogen pressure and the reaction time are adjusted according to the desired hydrogenation rate (iodine value). May be changed by changing.

After the completion of the hydrogenation reaction, excess hydrogen is released out of the system, and then the hydrogenation catalyst is removed. This can be performed, for example, by adding activated carbon to the reaction system, allowing the hydrogenation catalyst to be adsorbed on the activated carbon, and removing the hydrogenation catalyst by centrifugation, filtration, or the like. Further, an ion exchange resin may be used instead of activated carbon. Alternatively, the hydrogenation catalyst may be left as it is in the obtained nitrile group-containing highly saturated copolymer latex without removing it, and the process may proceed to the next step.

Next, when a solvent is used, it is removed by a known method such as a steel stripping method. The nitrile group-containing highly saturated copolymer rubber latex thus obtained is concentrated, if necessary, to a desired concentration. Concentration may be performed by an ordinary method using a rotary evaporator, a high-speed centrifuge, or the like.

(Nitrile Group-Containing Highly Saturated Copolymer Rubber Latex) The nitrile group-containing highly saturated copolymer rubber latex used in the present invention is obtained from the nitrile group-containing unsaturated copolymer rubber latex as described above. It is necessary that the iodine value of the contained highly saturated copolymer rubber is 120 or less. When the iodine value exceeds 120, the adhesive strength of the obtained adhesive composition is undesirably reduced.

(Adhesive Composition) The adhesive composition for vulcanizing and bonding the nitrile group-containing highly saturated copolymer rubber and the organic synthetic fiber of the present invention comprises the above nitrile group-containing highly saturated copolymer rubber latex and resorcinol. -A formaldehyde resin as an essential component.

As the resorcin-formaldehyde resin, conventionally known resins (for example, those disclosed in JP-A-55-142635) can be used without any particular limitation. Also, 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or a similar compound, isocyanate, blocked isocyanate, ethylene urea, polyepoxide, modified, which has been conventionally used to enhance the adhesive strength A polyvinyl chloride resin or the like can be used in combination.

In the adhesive composition of the present invention, the amount of resorcin-formaldehyde resin used (in terms of dry weight) is usually 10% of the solid content of the nitrile group-containing highly saturated copolymer rubber latex.
It is 10 to 180 parts by weight with respect to 0 parts by weight.

In addition, within the scope not impairing the spirit of the present invention, a part of the nitrile group-containing highly saturated copolymer rubber latex, styrene-butadiene copolymer rubber latex, its carboxy-modified latex, acrylonitrile butadiene copolymer rubber latex, The carboxy-modified latex, natural rubber latex or the like can be used.

(Treatment of Organic Synthetic Fibers with Adhesive Composition) The adhesive composition of the present invention can be suitably used for treating organic synthetic fibers.

The organic synthetic fiber that can be used in the present invention is not particularly limited, and specific examples thereof include polyvinyl alcohol fiber, polyester fiber, polyamide fiber, and aramid fiber (aromatic polyamide fiber).

Examples of the form of these fibers include staples, filaments, cords, ropes, and woven fabrics such as canvas, but other forms are also possible.

The method for treating fibers with the adhesive composition of the present invention is not particularly limited, and the same method as in the case of using a known resorcinol-formaldehyde resin-polymer latex-based adhesive composition can be employed. An example of the method is as follows. The fibers are dipped in the adhesive composition and, if necessary, usually at 100-150 ° C, 0.5
After drying under conditions of about 10 minutes, heat treatment is performed. The heating condition is not particularly limited, and is a time and a temperature sufficient for reacting and fixing the adhesive composition adhered by immersion, and is usually performed at about 140 to about 250 ° C. for several minutes. Prior to the immersion treatment of the fiber, the fiber may be immersed in an isocyanate solution, an epoxy solution or a mixed solution thereof and dried in advance.

In the present invention, the adhesion amount of the solid content of the adhesive composition is not particularly limited, but is usually 2 to 20% by weight, preferably 3 to 10% by weight based on the fiber.

(Method of Adhering Organic Synthetic Fiber to Nitrile Group-Containing Highly Saturated Copolymer Rubber Using Adhesive Composition) The adhesive composition of the present invention comprises a vulcanization method between an organic synthetic fiber and a nitrile group-containing highly saturated copolymer rubber. It can be effectively used for adhesion, whereby a composite of an organic synthetic fiber and a nitrile group-containing highly saturated copolymer rubber having excellent adhesive strength can be obtained.

The nitrile group-containing highly saturated copolymer rubber (hereinafter, sometimes referred to as adherend rubber) used as the adherend of the organic synthetic fiber in the present invention comprises α, β-ethylenically unsaturated nitrile and conjugated diene. And / or a copolymer rubber with an ethylenically unsaturated monomer or a derivative thereof. The content of the monomer unit containing a nitrile group in the adherend rubber is usually determined from the viewpoint of the oil resistance of the rubber product combined with the fiber.
It is in the range of 10-60% by weight, and the iodine value is
The range is 120 or less, preferably 100 or less, and more preferably 80 or less. In the synthesis of the adherend rubber, the same monomers as those used in the synthesis of the nitrile group-containing unsaturated copolymer rubber latex can be used.

The adherend rubber can be directly obtained as a nitrile group-containing highly saturated copolymer rubber by a copolymer of each of the above monomers, or can be obtained by hydrogenating a nitrile group-containing unsaturated copolymer rubber. it can. The polymerization method and hydrogenation method therefor are not particularly limited either. Specific examples of the adherend rubber include:
Highly saturated butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-acrylonitrile copolymer rubber; highly saturated butadiene-methyl acrylate-acrylonitrile copolymer rubber, highly saturated butadiene- Acrylic acid-acrylonitrile copolymer rubber, highly saturated butadiene
Examples thereof include ethylene-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl acrylate-vinyl norbornene-acrylonitrile copolymer rubber, and the like.

The method of vulcanization bonding between the nitrile group-containing highly saturated copolymer rubber and the organic synthetic fiber treated with the adhesive composition of the present invention is not particularly limited, and is conventionally used for vulcanization bonding between rubber and fiber. The same method can be adopted. Specifically, it is achieved by embedding organic synthetic fibers in a rubber compound prepared by adding a compounding agent such as a vulcanizing agent and a filler to rubber, followed by vulcanization. The vulcanization conditions are usually at 120 to 180 ° C. for 1 to 120 minutes under a pressure of 0.5 to 10 MPa.

〔The invention's effect〕

Thus, the composite of the nitrile group-containing highly saturated copolymer rubber and the organic synthetic fiber obtained by using the adhesive composition of the present invention has excellent initial properties as compared with the case of using the conventional adhesive composition. Since it has adhesive strength, adhesive strength after heat aging (heat resistant adhesive strength) and water resistant adhesive strength, various belts such as toothed conductive belts and V belts using organic synthetic fibers as tensile members, pressure hoses, freon hoses, etc. It is useful for manufacturing various hoses.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. The parts and percentages in the examples are on a weight basis unless otherwise specified.

(Preparation of latex by emulsion polymerization method) 240 parts of water, 4 parts of potassium oleate, and 37 parts of acrylonitrile were put in this order in a pressure-resistant bottle having a capacity of 1000 ml, the inside of the bottle was replaced with nitrogen gas, and then 63 parts of butadiene was pressed. did. This bottle is placed in a thermostatic water bath, 0.25 parts of ammonium persulfate is added as a catalyst, polymerization is carried out for 16 hours, and latex A- of an acrylonitrile-butadiene copolymer (hereinafter abbreviated as NBR) having a bound acrylonitrile content of 37% by weight. 5 was obtained.

Next, after adjusting the solid content concentration of this to 12%,
400 ml of the mixture was put into an autoclave having an internal volume of 1 equipped with a stirrer, and nitrogen gas was flown for 10 minutes to remove dissolved oxygen in the latex. Then, palladium acetate as a hydrogenation catalyst was dissolved in 240 ml of acetone and added. After the atmosphere in the system was replaced twice with hydrogen gas, the system was pressurized with hydrogen gas until the pressure in the system reached 30 atm. Thereafter, the contents were heated to 50 ° C. and reacted for 6 hours with stirring. After cooling the content to room temperature, excess hydrogen is purged, and the obtained latex is removed with an evaporator to remove the organic solvent,
It was concentrated until the solid content became about 40% to obtain a highly saturated NBR latex A-1 having an iodine value of 108.

Except for changing the hydrogenation conditions (reaction time and / or amount of catalyst used), the same procedure as above was carried out to obtain a highly saturated NB having a different iodine value.
R latexes A-2 and A-3 and NBR latex A-4 having a high degree of unsaturation were obtained. Table 1 shows the pH and average particle size of these latexes and the iodine value of NBR.

(Preparation of latex by phase inversion method) NBR obtained by coagulating a latex of NBR having a bound acrylonitrile amount of 36% obtained by an emulsion polymerization method in the same manner as described above in a usual manner is dissolved in methyl isobutyl ketone, and palladium is dissolved. Hydrogenation of the butadiene moiety in the NBR using a carbon catalyst to give a hydrogenated NBR with an iodine value of 80; This hydrogenated N
60 parts of BR were dissolved in 540 parts of a mixed solvent of methyl ethyl ketone / cyclohexane (50/50% by volume). The obtained solution is stirred with a homomixer (M type manufactured by Tokushu Kika Kogyo),
After adding 32 parts of a 15% strength aqueous solution of potassium oleate adjusted to pH 11.5 with potassium hydroxide and 600 parts of water, 1
The mixture was emulsified by stirring at 2000 rpm for 10 minutes. The solvent was removed from the produced emulsion by steam stripping, and then concentrated using an evaporator to obtain a latex having a solid content of about 30%. In addition, this is
Centrifugation at 000 rpm for 16 minutes (Type H made by domestic centrifuge)
251) to obtain latex B-1 having a solid content of 40%. Similarly, latex B-2 having a solid content of about 40% was obtained from hydrogenated NBR having an iodine value of 28. Table 2 shows the properties of the obtained latex.

(Preparation of adherend rubber compound) According to the compounding recipe shown in Table 3, the nitrile group-containing highly saturated copolymer rubber and the compounding agent were kneaded on a roll, and about 2.5 m
A sheet of rubber compound having a thickness of m was made.

Example 1 An adhesive composition was prepared using the latex described in Tables 1 and 2 according to the formulation shown in Table 4.

Using this adhesive composition, a nylon cord (nylon 6, structure 1890d /
After immersion treatment of 2), heat treatment was performed at 200 ° C. for 2 minutes.

The treatment cord obtained in this manner is embedded in an adherend rubber compound with an embedded length of 8 mm, and the rubber compound (a)
The mixture was vulcanized at a press pressure of 5 MPa and 150 ° C. for 30 minutes, and the rubber compound (b) was vulcanized at a press pressure of 5 MPa and 160 ° C. for 30 minutes to obtain a composite of fiber and rubber.

The obtained composite was subjected to a cord pull-out test according to ASTM D2138-72 and the like to measure the initial adhesive strength. The composite obtained in the same manner was heat-treated in an air oven at 120 ° C. for 168 hours, and then subjected to a cord pull-out test to measure the heat-resistant adhesive strength. In addition, the complex obtained in the same manner
The adhesive strength after standing in hot water at 50 ° C. for 72 hours (water-resistant adhesive strength) was measured. Table 5 shows the results.

From the results shown in Table 5, the use of the adhesive composition of the present invention allows the use of the organic synthetic fiber and the nitrile group-containing highly saturated copolymer rubber excellent in initial adhesive strength, heat resistant adhesive strength and water resistant adhesive strength. Whereas a composite is obtained, when an adhesive composition prepared from a latex obtained by a phase inversion method is used,
It can be seen that the resulting composite has poor water-resistant adhesive strength.

Example 2 An adhesive composition was prepared from the latexes shown in Tables 1 and 2 according to the formulation shown in Table 6.

A polyester cord (structure 1100d / 2 × 3) was immersed in a single cord dip machine for testing using the adhesive composition obtained according to the formulation shown in Table 6, and then heat-treated at 245 ° C. for 1 minute. The obtained cord was immersed in the adhesive composition obtained according to the formulation shown in Table 4 and then heat-treated at 245 ° C. for 1 minute.

From the polyester cord thus obtained, a composite of fiber and rubber was prepared in the same manner as in Example 1, and the same cord pull-out test as in Example 1 was performed. The results are shown in Table 7.

From the results shown in Table 7, it can be seen that, even when polyester is used as the fiber, an organic synthetic fiber-nitrile group-containing highly saturated copolymer rubber composite having excellent water resistance can be obtained according to the present invention.

Example 3 Aramid cord (Kevlar manufactured by DuPont, structure 1500d /
2) was heat-treated at 220 ° C. for 1 minute using a pretreatment liquid shown in Table 8 with a test single cord dip machine.

The obtained cord was further immersed in the adhesive composition obtained according to the formulation shown in Table 4 and then treated at 250 ° C. for 1 minute. From the aramid cord thus obtained, a composite of fiber and rubber was prepared in the same manner as in Example 1, and the same cord pull-out test as in Example 1 was performed. The results are shown in Table 9.

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Claims (3)

(57) [Claims] 1. An adhesive composition of an organic synthetic fiber and a nitrile group-containing highly saturated copolymer rubber containing a nitrile group-containing highly saturated copolymer rubber latex having an iodine value of 120 or less and a resorcinol-formaldehyde resin. In the product, a nitrile group-containing highly saturated copolymer rubber latex is obtained by treating the nitrile group-containing unsaturated copolymer rubber latex obtained by the emulsion polymerization method with hydrogen in the presence of a hydrogenation catalyst, whereby the latex is obtained. An adhesive composition characterized by being obtained by selectively hydrogenating a carbon-carbon double bond in a constituent nitrile group-containing unsaturated copolymer. 2. A method for treating organic synthetic fibers, comprising treating with the adhesive composition according to claim 1. 3. An organic compound characterized by treating the organic synthetic fiber with the adhesive composition of claim (1) when vulcanizing and bonding the nitrile group-containing highly saturated copolymer rubber and the organic synthetic fiber. Bonding method between synthetic fiber and rubber.